White ink composition for ink-based digital printing

FIELD OF DISCLOSURE

0001The disclosure relates to ink-based digital printing. In particular, this disclosure relates to white inks suitable for ink-based digital printing, among other printing applications.

BACKGROUND

0002Conventional lithographic printing techniques cannot accommodate true high-speed variable data printing processes in which images to be printed change from impression to impression, for example, as enabled by digital printing systems. The lithography process is often relied upon, however, because it provides very high quality printing due to the quality and color gamut of the inks used. Lithographic inks are also less expensive than other inks, toners, and many other types of printing or marking materials.

0003Ink-based digital printing uses a variable data lithography printing system, or digital offset printing system. A “variable data lithography system” is a system that is configured for lithographic printing using lithographic inks and based on digital image data, which may be variable from one image to the next. “Variable data lithography printing,” or “digital ink-based printing,” or “digital offset printing” is lithographic printing of variable image data for producing images on a substrate that are changeable with each subsequent rendering of an image on the substrate in an image forming process.

0004For example, a digital offset printing process may include transferring radiation-curable ink onto a portion of a fluorosilicone-containing imaging member or printing plate that has been selectively coated with a dampening fluid layer according to variable image data. The ink is then transferred from the printing plate to a substrate such as paper, plastic, or metal on which an image is being printed and cured. The same portion of the imaging plate may be optionally cleaned depending on ink type and used to make a succeeding image that is different than the preceding image, based on the variable image data.

0005Digital offset printing inks differ from conventional inks because they must meet demanding rheological requirements imposed by the lithographic printing process while being compatible with system component materials and meeting the functional requirements of sub-system components, including wetting and transfer.

SUMMARY

0006Digital offset inks are provided that are radiation-curable, compatible with ink-based digital printing system components, and have high transfer efficiency, which reduces ghosting of previously printed images if a cleaning system is not used. Digital offset inks contain much higher (up to 10 times, for example, or 10% to 50% by weight of the total weight of the ink composition) pigment loading, and therefore have higher viscosity at room temperature and the temperature of application during a printing process. Methods for manufacturing digital offset inks having high pigment loading and, optionally, high viscosities have been provided. For example, U.S. patent application Ser. No. 13/474,185, titled “Methods For Manufacturing Curable Inks For Digital Offset Printing Applications And The Inks Made Therefrom,” filed on May 17, 2012, by Lee et al., the disclosure of which is hereby incorporated by reference herein in its entirety, discloses UV curable ink compositions and methods for the manufacture thereof that do not gel, contain a high pigment load, and can have a high viscosity that is advantageous for digital offset printing.

0007Related art inks including traditional offset inks can present the following challenges: solubility in the dampening fluid, swelling of the silicone layer on the imaging member, poor release properties from the imaging member, and limited curing performance. Digital offset inks must be compatible with a surface layer of the imaging member. For example, the ink composition should not swell and deform the silicone, fluorosilicone, and/or VITON-containing imaging member surface layer, thereby causing image quality defects. The digital offset ink should also be formulated for adhering to portions of the imaging member surface. For example, such surface layer portions include those from which dampening fluid has been removed during a lithographic printing process, after laser patterning of a dampening fluid layer applied to the imaging member surface layer.

0008Further, digital offset ink must be compatible with dampening fluids such as octamethylcyclotetrasiloxane (cyclotetrasiloxane, “D4”) and decamethylcyclopentasiloxane (cyclopentasiloxane, “D5”), and not mixing with the dampening fluid thereby affecting background areas, or portions of the imaging member surface from which dampening fluid has not been removed after laser patterning.

0009Digital offset ink compositions have been provided that have certain wetting and release properties that are useful with the re-imageable imaging member of digital offset systems, and that are also compatible with non-aqueous dampening fluids. For example, U.S. patent application Ser. No. 13/474,138, titled “Inks For Offset Digital Printing Applications,” filed on May 17, 2012, by Breton et al., the disclosure of which is incorporated herein by reference in its entirety, discloses ink compositions having desired solubility parameters that are compatible with dampening fluids.

0010Other ink compositions suitable for ink-based digital printing have been developed. For example, U.S. patent application Ser. No. 13/473,791, titled “Fluorescent Security Enabled Ink For Digital Offset Printing Applications,” filed on May 17, 2012, by Iftime et al., the disclosure of which is incorporated herein by reference in its entirety, discloses an ink composition useful for digital offset printing applications comprises a fluorescent colorant and a plurality of curable compounds. The compounds have desirable Hansen solubility parameters are as described herein, and the ink composition is both compatible with certain dampening fluids and has certain rheological properties, including a low viscosity. The fluorescent ink composition is useful for printing security features at high speed in short runs with customized data to produce anti-counterfeit packaging.

0011Also, U.S. patent application Ser. No. 13/473,921, titled “Photochromic Security Enabled Ink for Digital Offset Printing Applications,” filed on May 17, 2012, by Iftime et al., the disclosure of which is incorporated herein by reference in its entirety, discloses certain photochromic ink compositions which are compatible with dampening fluids and are useful for providing security information in variable data lithographic printing applications.

0012New radiation curable ink designs for digital offset inks are desired, however, for enhanced ink-based digital printing. It has been found that available inks for ink-based digital printing suffer from shortfalls relating to solubility with dampening fluid, image background issues, high cost requirements, a narrow design space. Improved inks are provided that meet wetting and release requirements while being compatible with non-aqueous dampening fluid, and tending not to swell a silicone-containing imaging member surface are provided. Moreover, inks are provided that enable highly efficient ink transfer from an ink delivery system such as an anilox roll during a printing process while avoiding image quality defects in a resulting printed image.

0013White radiation curable ink compositions are provided for expanding ink-based digital printing capabilities for printing processes. For example, white inks in accordance with embodiments enable enhanced label processing. White ink compositions in accordance with embodiments meet subsystem requirements that are unique to variable data lithography and architecture such as those discussed above. Ink compositions of embodiments satisfy crucial wetting and release property requirements, and may be compatible with non-aqueous dampening fluids. Moreover, ink compositions of embodiments are suitable for anilox roll ink delivery to a digital offset imaging member. In some systems and embodiments, ink compositions of embodiments may be partially cured prior to transfer.

0014Exemplary embodiments are described herein. It is envisioned, however, that any system that incorporates features of systems described herein are encompassed by the scope and spirit of the exemplary embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

0015<figref idref="DRAWINGS">FIG. 1</figref> shows a side diagrammatical view of a related art ink-based digital printing system;

0016<figref idref="DRAWINGS">FIG. 2</figref> shows IR spectra for white digital offset ink in accordance with embodiments.

DETAILED DESCRIPTION

0017Exemplary embodiments are intended to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the apparatus and systems as described herein.

0018The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). When used with a specific value, it should also be considered as disclosing that value.

0019Reference is made to the drawings to accommodate understanding of systems for ink-based digital printing using inks in accordance with embodiments. In the drawings, like reference numerals are used throughout to designate similar or identical elements. The drawings depict exemplary systems for ink-based digital printing, and data associated with an exemplary white ink composition in accordance with an embodiment.

0020White ink compositions in accordance with embodiments are not limited to use ink-based digital printing systems. Digital offset inks disclosed herein may be useful in conventional offset printing or hybrid conventional offset and digital offset printing systems. Nonetheless, white digital offset inks of embodiments meet systems requirements that are unique to digital offset printing systems. In particular, inks of embodiments satisfy wetting and release requirements imposed by the re-imageable imaging member of ink-based digital printing systems. Further, inks of embodiments are compatibility with dampening fluids suitable for ink-based digital printing, including non-aqueous dampening fluids. Inks of embodiments are enabled for transfer from an ink delivery system such as anilox roll to the imaging member, e.g., reimageable offset plate.

0021Exemplary variable data lithography systems are disclosed in U.S. patent application Ser. No. 13/095,714 (“714 application”), titled “Variable Data Lithography System,” filed on Apr. 27, 2011, by Stowe et al., the disclosure of which is hereby incorporated by reference herein in its entirety. The systems and methods disclosed in the 714 application are directed to improvements on various aspects of previously-attempted variable data imaging lithographic marking concepts based on variable patterning of dampening fluids to achieve effective truly variable digital data lithographic printing.

0022A general description of an exemplary ink-based digital printing system <b>100</b> as shown in <figref idref="DRAWINGS">FIG. 1</figref> is provided here. Additional details regarding individual components and/or subsystems shown in the exemplary system <b>100</b> of <figref idref="DRAWINGS">FIG. 1</figref> may be found in the 714 application.

0023As shown in <figref idref="DRAWINGS">FIG. 1</figref>, the exemplary system <b>100</b> may include an imaging member <b>110</b>. The imaging member <b>110</b> in the embodiment shown in <figref idref="DRAWINGS">FIG. 1</figref> is a drum, but this exemplary depiction should not be interpreted so as to exclude embodiments wherein the imaging member <b>110</b> includes a drum, plate or a belt, or another now known or later developed configuration. The reimageable surface may be formed of materials including, for example, a class of materials commonly referred to as silicones, including polydimethylsiloxane (PDMS), among others. The reimageable surface may be formed of a relatively thin layer over a mounting layer, a thickness of the relatively thin layer being selected to balance printing or marking performance, durability and manufacturability.

0024The imaging member <b>110</b> is used to apply an ink image to an image receiving media substrate <b>114</b> at a transfer nip <b>112</b>. The transfer nip <b>112</b> is formed by an impression roller <b>118</b>, as part of an image transfer mechanism <b>160</b>, exerting pressure in the direction of the imaging member <b>110</b>. Image receiving medium substrate <b>114</b> should not be considered to be limited to any particular composition such as, for example, paper, plastic, or composite sheet film. The exemplary system <b>100</b> may be used for producing images on a wide variety of image receiving media substrates. The 714 application also explains the wide latitude of marking (printing) materials that may be used, including marking materials with pigment densities greater than 10% by weight. As does the 714 application, this disclosure will use the term ink to refer to a broad range of printing or marking materials to include those which are commonly understood to be inks, pigments, and other materials which may be applied by the exemplary system <b>100</b> to produce an output image on the image receiving media substrate <b>114</b>.

0025The 714 application depicts and describes details of the imaging member <b>110</b> including the imaging member <b>110</b> being comprised of a reimageable surface layer formed over a structural mounting layer that may be, for example, a cylindrical core, or one or more structural layers over a cylindrical core.

0026The exemplary system <b>100</b> includes a dampening fluid system <b>120</b> generally comprising a series of rollers, which may be considered as dampening rollers or a dampening unit, for uniformly wetting the reimageable surface of the imaging member <b>110</b> with dampening fluid. A purpose of the dampening fluid system <b>120</b> is to deliver a layer of dampening fluid, generally having a uniform and controlled thickness, to the reimageable surface of the imaging member <b>110</b>. As indicated above, it is known that a dampening fluid such as fountain solution may comprise mainly water optionally with small amounts of isopropyl alcohol or ethanol added to reduce surface tension as well as to lower evaporation energy necessary to support subsequent laser patterning, as will be described in greater detail below. Small amounts of certain surfactants may be added to the fountain solution as well. Alternatively, other suitable dampening fluids may be used to enhance the performance of ink based digital lithography systems. Exemplary dampening fluids include water, Novec 7600 (1,1,1,2,3,3-Hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxyl)pentane and has CAS#870778-34-0.), and D4 (octamethylcyclotetrasiloxane). Other suitable dampening fluids are disclosed, by way of example, in co-pending U.S. patent application Ser. No. 13/284,114, filed on Oct. 28, 2011, titled “Dampening Fluid For Digital Lithographic Printing,” the disclosure of which is hereby incorporated herein by reference in its entirety.

0027Once the dampening fluid is metered onto the reimageable surface of the imaging member <b>110</b>, a thickness of the dampening fluid may be measured using a sensor <b>125</b> that may provide feedback to control the metering of the dampening fluid onto the reimageable surface of the imaging member <b>110</b> by the dampening fluid system <b>120</b>.

0028After a precise and uniform amount of dampening fluid is provided by the dampening fluid system <b>120</b> on the reimageable surface of the imaging member <b>110</b>, and optical patterning subsystem <b>130</b> may be used to selectively form a latent image in the uniform dampening fluid layer by image-wise patterning the dampening fluid layer using, for example, laser energy. Typically, the dampening fluid will not absorb the optical energy (IR or visible) efficiently. The reimageable surface of the imaging member <b>110</b> should ideally absorb most of the laser energy (visible or invisible such as IR) emitted from the optical patterning subsystem <b>130</b> close to the surface to minimize energy wasted in heating the dampening fluid and to minimize lateral spreading of heat in order to maintain a high spatial resolution capability. Alternatively, an appropriate radiation sensitive component may be added to the dampening fluid to aid in the absorption of the incident radiant laser energy. While the optical patterning subsystem <b>130</b> is described above as being a laser emitter, it should be understood that a variety of different systems may be used to deliver the optical energy to pattern the dampening fluid.

0029The mechanics at work in the patterning process undertaken by the optical patterning subsystem <b>130</b> of the exemplary system <b>100</b> are described in detail with reference to <figref idref="DRAWINGS">FIG. 5</figref> in the 714 application. Briefly, the application of optical patterning energy from the optical patterning subsystem <b>130</b> results in selective removal of portions of the layer of dampening fluid.

0030Following patterning of the dampening fluid layer by the optical patterning subsystem <b>130</b>, the patterned layer over the reimageable surface of the imaging member <b>110</b> is presented to an inker subsystem <b>140</b>. The inker subsystem <b>140</b> is used to apply a uniform layer of ink over the layer of dampening fluid and the reimageable surface layer of the imaging member <b>110</b>. The inker subsystem <b>140</b> may use an anilox roller to meter an offset lithographic ink onto one or more ink forming rollers that are in contact with the reimageable surface layer of the imaging member <b>110</b>. Separately, the inker subsystem <b>140</b> may include other traditional elements such as a series of metering rollers to provide a precise feed rate of ink to the reimageable surface. The inker subsystem <b>140</b> may deposit the ink to the pockets representing the imaged portions of the reimageable surface, while ink on the unformatted portions of the dampening fluid will not adhere to those portions.

0031The cohesiveness and viscosity of the ink residing in the reimageable layer of the imaging member <b>110</b> may be modified by a number of mechanisms. One such mechanism may involve the use of a rheology (complex viscoelastic modulus) control subsystem <b>150</b>. The rheology control system <b>150</b> may form a partial crosslinking layer of the ink on the reimageable surface to, for example, increase ink cohesive strength relative to the reimageable surface layer. Curing mechanisms may include optical or photo curing, heat curing, drying, or various forms of chemical curing. Cooling may be used to modify rheology as well via multiple physical cooling mechanisms, as well as via chemical cooling.

0032The ink is then transferred from the reimageable surface of the imaging member <b>110</b> to a substrate of image receiving medium <b>114</b> using a transfer subsystem <b>160</b>. The transfer occurs as the substrate <b>114</b> is passed through a nip <b>112</b> between the imaging member <b>110</b> and an impression roller <b>118</b> such that the ink within the voids of the reimageable surface of the imaging member <b>110</b> is brought into physical contact with the substrate <b>114</b>. With the adhesion of the ink having been modified by the rheology control system <b>150</b>, modified adhesion of the ink causes the ink to adhere to the substrate <b>114</b> and to separate from the reimageable surface of the imaging member <b>110</b>. Careful control of the temperature and pressure conditions at the transfer nip <b>112</b> may allow transfer efficiencies for the ink from the reimageable surface of the imaging member <b>110</b> to the substrate <b>114</b> to exceed 95%. While it is possible that some dampening fluid may also wet substrate <b>114</b>, the volume of such a dampening fluid will be minimal, and will rapidly evaporate or be absorbed by the substrate <b>114</b>.

0033In certain offset lithographic systems, it should be recognized that an offset roller, not shown in <figref idref="DRAWINGS">FIG. 1</figref>, may first receive the ink image pattern and then transfer the ink image pattern to a substrate according to a known indirect transfer method.

0034Following the transfer of the majority of the ink to the substrate <b>114</b>, any residual ink and/or residual dampening fluid must be removed from the reimageable surface of the imaging member <b>110</b>, preferably without scraping or wearing that surface. An air knife may be employed to remove residual dampening fluid. It is anticipated, however, that some amount of ink residue may remain. Removal of such remaining ink residue may be accomplished through use of some form of cleaning subsystem <b>170</b>. The 714 application describes details of such a cleaning subsystem <b>170</b> including at least a first cleaning member such as a sticky or tacky member in physical contact with the reimageable surface of the imaging member <b>110</b>, the sticky or tacky member removing residual ink and any remaining small amounts of surfactant compounds from the dampening fluid of the reimageable surface of the imaging member <b>110</b>. The sticky or tacky member may then be brought into contact with a smooth roller to which residual ink may be transferred from the sticky or tacky member, the ink being subsequently stripped from the smooth roller by, for example, a doctor blade.

0035The 714 application details other mechanisms by which cleaning of the reimageable surface of the imaging member <b>110</b> may be facilitated. Regardless of the cleaning mechanism, however, cleaning of the residual ink and dampening fluid from the reimageable surface of the imaging member <b>110</b> is essential to preventing ghosting in the proposed system. Once cleaned, the reimageable surface of the imaging member <b>110</b> is again presented to the dampening fluid system <b>120</b> by which a fresh layer of dampening fluid is supplied to the reimageable surface of the imaging member <b>110</b>, and the process is repeated.

0036Before transfer of an ink image to an image receiving substrate or print medium, the ink image may be partially cured at a partial UV cure subsystem. White ink compositions of embodiments are suitable for ink-based digital printing using partial cure.

0037As discussed above, digital offset ink must possess physical and chemical properties that are specific to ink-based digital printing systems. The ink must be compatible with materials that it comes in contact with, including the imaging plate and dampening fluid, and printable substrates such as paper, metal, or plastic. The ink must also meet all functional requirements of the subsystems including wetting and transfer properties defined by subsystem architecture and material sets.

0038Inks formulated for ink-based digital printing, or digital offset inks, are different in many ways from other inks developed for printing applications, including pigmented solvents, UV gel inks, and other inks. For example, digital offset inks contain much higher pigment and therefore have higher viscosity at room temperature than other inks, which can make ink delivery by way of an anilox roll or inkjet system difficult. Digital offset inks must meet certain wetting and release property requirements imposed by the imaging member used for ink-based digital printing processes, while being compatible with non-aqueous dampening fluid options.

0039The inks described herein may include the following components: (a) radiation-curable functional acrylate monomer compounds, including mono-, di-, and tri-functional acrylate monomers, oligomers; (b) dispersants; (c) pigments; (d) clays; (e) initiators; (f) additional curable compounds including monomers, oligomers, including oligomers from SARTOMER USA, LLC or CYTEC Industries, Inc., prepolymers, polymers; (g) additives including surfactants, free-radical scavengers, and the like.

0040The radiation curable monomer (a) may be added in any suitable amount. For example, the monomer or oligomer can be present in any suitable amount. In embodiments, the monomer or oligomer, or combination thereof is added in an amount of from about 10 to about 85%, or from about 30 to about 80%, or from about 50 to about 70%, by weight based on the total weight of the curable ink composition.

0041The dispersant components (b) may include any suitable or desired dispersant including, but not limited to AB-diblock copolymers of high molecular weight such as EFKA® 4340 available from BASF SE, and DISPERBYK® 2100 available from Byk-Chemie GmbH, or a mixture thereof. In a specific embodiment, the dispersant mixture comprises a cyclohexane dimethanol diacrylate (such as CD406® available from Sartomer USA, LLC) and at least one additional component, such as EFKA® 4340 is a high molecular weight dispersing agent having an AB-diblock copolymer structure available from BASF SE. In an exemplary embodiment, the dispersant is a polymeric dispersant, such as SOLSPERSE® 39000, commercially available from The Lubrizol Corporation. The dispersant may be added in an amount within the range of from about 10% to about 80% by weight, based on the weight of pigment in the composition.

0042The disclosed curable ink composition also includes a colorant or pigment component (c), which may be any desired or effective colorant may be employed, including pigments, mixtures of pigments, mixtures of pigments and dyes, and the like, provided that the colorant may be dissolved or dispersed in the at least one monomer and at least one dispersant. In specific embodiments, the colorant is a pigment. Examples of suitable pigments include titanium dioxide, TiO₂. TiO₂is commercially available from DuPont, TI-PURE series of pigments, while both anatase and rutile titanium dioxide can be used, the rutile crystal structure is preferred, optimum particle size is preferred to be in the 200 to 300 nanometers. The disclosed curable ink composition may also contain in addition to titanium dioxide, one of more of the following additives: clay, silica, magnesium silicate or zinc oxide.

0043For example, a white ink composition in accordance with an exemplary embodiment may include the following components: a white pigment, DuPont Ti-PURE Tio₂, having an oil absorption of 15.0 and pH=8.2, and LAB values of 99.66, −0.58, and 2.05, respectively; curable functional acrylate monomers available from SARTOMER, including CN 293, CN294E, CN259, CN454; SOLSPERSE® 39000 dispersant from Lubrizol; a thermal stabilizer, IRGASTAB UV10 available from BASF; aerosol 200 vs available from Degussa Canada Ltd; and a photoinitiator system composed of IRGACURE 819, Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide), and IRGACURE 184, 1-Hydroxy-cyclohexyl-phenyl-ketone. The photoinitiator system may include IRGACURE 379, 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and ESACURE Kip 150, Oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] available from BASF, BASF, and Lamberti, respectively. Other components or additives may include: polyester oligomers selected from Sartomer, CN2255, a high viscosity polyester acrylate oligomer with a glass transition T of −13 degrees Celsius, and CN2256, also a polyester acrylate oligomer with viscosity of 11,000 cps at 60 degrees Celsius, and a glass transition T of −22 degrees Celsius; an hindered amine light stabilizer such as TINUVIN 292; a levelling agent such as BYK 3500, a polyether modified acryl functional polydimethylsiloxane; and a defoamer, ADDITOL VXL 4951 available from Cytek.

0044Two radiation curable white digital offset inks in accordance with embodiments were produced and tested. The inks were prepared by the process disclosed by Lee et al. in the 185 application. Exemplary formulations are disclosed in Table 1.

0045<tables id="TABLE-US-00001" num="00001"><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="1"><colspec colname="1" colwidth="217pt" align="center" /><thead><row><entry namest="1" nameend="1" rowsep="1">TABLE 1</entry></row></thead><tbody valign="top"><row><entry namest="1" nameend="1" align="center" rowsep="1" /></row><row><entry>White Digital Offset Ink</entry></row></tbody></tgroup><tgroup align="left" colsep="0" rowsep="0" cols="4"><colspec colname="offset" colwidth="14pt" align="left" /><colspec colname="1" colwidth="84pt" align="left" /><colspec colname="2" colwidth="49pt" align="center" /><colspec colname="3" colwidth="70pt" align="center" /><tbody valign="top"><row><entry /><entry /><entry>White_1 (W1)</entry><entry>White_2 (W2)</entry></row><row><entry /><entry>Chemical</entry><entry>wt %</entry><entry>wt %</entry></row><row><entry /><entry namest="offset" nameend="3" align="center" rowsep="1" /></row></tbody></tgroup><tgroup align="left" colsep="0" rowsep="0" cols="4"><colspec colname="offset" colwidth="14pt" align="left" /><colspec colname="1" colwidth="84pt" align="left" /><colspec colname="2" colwidth="49pt" align="char" char="." /><colspec colname="3" colwidth="70pt" align="char" char="." /><tbody valign="top"><row><entry /><entry>TiO2</entry><entry>35.00</entry><entry>35.00</entry></row><row><entry /><entry>Sartomer CN293</entry><entry>4.00</entry><entry>0.00</entry></row><row><entry /><entry>Sartomer CN294E</entry><entry>0.00</entry><entry>43.35</entry></row><row><entry /><entry>Sartomer SR259</entry><entry>32.00</entry><entry>9.50</entry></row><row><entry /><entry>Sartomer SR454</entry><entry>16.00</entry><entry>0.00</entry></row><row><entry /><entry>Lubrizol Solsperse 39000</entry><entry>5.25</entry><entry>5.25</entry></row><row><entry /><entry>Southern Clay HY</entry><entry>1.70</entry><entry>1.70</entry></row><row><entry /><entry>Ciba IRGACURE 184</entry><entry>2.92</entry><entry>3.00</entry></row><row><entry /><entry>Ciba IRGACURE 819</entry><entry>2.10</entry><entry>2.00</entry></row><row><entry /><entry>Ciba IRGASTAB UV10</entry><entry>0.20</entry><entry>0.20</entry></row><row><entry /><entry>BYK3500</entry><entry>0.83</entry><entry>0.00</entry></row><row><entry /><entry>Total</entry><entry>100.00</entry><entry>100.00</entry></row><row><entry /><entry>Zero Shear Viscosity, cps</entry><entry>1.33 × 10^{{circumflex over ( )}}6 </entry><entry>4.25 × 10{circumflex over ( )}5</entry></row><row><entry /><entry>Viscosity, 5 sec−1</entry><entry>2.2 × 10^{{circumflex over ( )}}3</entry><entry>4.32 × 10{circumflex over ( )}4</entry></row><row><entry /><entry>Viscosity, 50 sec−1</entry><entry>7.2 × 10^{{circumflex over ( )}}2</entry><entry> 3.6 × 10{circumflex over ( )}4</entry></row><row><entry /><entry>Shear Thinning Index</entry><entry>0.33</entry><entry>0.83</entry></row><row><entry /><entry namest="offset" nameend="3" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

0046Exemplary formulations are shown in Table 1, and do not limit the scope of disclosure. Ink formulations made in accordance with the two inks shown in Table 1 were characterized to determine rheology. The shear viscosities of samples were measured using an Ares G2 controlled-strain rheometer having 25 mm parallel plate geometry, set at 0.5 mm gap and 25° C. such that the applied shear rate sweep ranged from 0.0001 to 500 s⁻¹. An ARES G2 controlled strain rheometer with a PELTIER temperature control (25MN, 0.02 RAD cone plate) for rapid heating and cooling was used for obtaining the rheology data. A flow sweep test procedure was run at 25° C., at a shear rate of 1.0E+−04 to 500 1/sec.

0047The printing performance of the radiation curable white digital offset ink was tested using hand testing. For example, the W2 ink formulation shown in Table 1 was applied by a hand roller or brushed to fluorosilicone-over-silicone test-plates and observed to wet the plate. D4 dampening fluid was applied to the plate before inking. The white ink did not adhere to the dampening fluid covered portion of the fluorosilicone. A corresponding ink image was transferred to black paper to form a transferred ink image demonstrating good background performance. The immediate transfer to paper resulted in splitting of ink at an observed 50% transfer efficiency. The application of D4 dampening fluid to the imaging plate, followed by rolling ink over the plate with a rubber roller and transferred to paper, demonstrated good background performance wherein white ink is not present in the background area that corresponds to the dampening fluid-coated portion of the fluorosilicone containing imaging plate.

0048Performing light partial curing, for example, using fluorescent room lighting fixture for 24 hours, resulted in efficient transfer of white ink to paper in further tests, above about 90% transfer efficiency, and full transfer of the ink in some embodiments. Slower curing at low intensity, or surrogate curing, may be easily scaled to higher intensity and short exposure time. The partially cured ink was still wet and smeared to the touch. A controlled experiment of ink left for 72 hours in the dark resulted in a 50% transfer efficiency, indicating that UV-induced curing enhances ink transfer. Transfer efficiency may be further optimized through appropriate selection of curable components and leveling agent, and by controlling ink delivery process to obtain images of appropriate thickness.

0049<figref idref="DRAWINGS">FIG. 2</figref> shows an infrared spectra of white inks that are (a) uncured, (b) partially cured sufficient for transfer, and (c) fully cured. The uncured, partially cured, and fully cured white digital offset inks were measured by FTIR to determine extent of cure. The top and bottom of the partially cured layers were measured, and were found to display the same spectrum. The uncured inks display IR absorptions for the carbonyl and vinyl peaks at 1700 and 1600 cm-1, respectively. The fully cured ink displays 100% reduction of vinyl peaks. The partially cured inks exhibit less than 10% reduction of the peaks, indicating 10% curing of the ink, or less, to be sufficient for transfer. Color and gloss measurements of the white inks are as follows: L*=96.94; A*=−0.05; B*=4.22; and 60% gloss=24.

0050It will be appreciated that the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also, various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art.